Manufacture of new azodyestuffs



Patented Aug. 18, 1931 UNITED STATES LEOPOLD LASKA AND ARTHUR ZI'ISCHER,

TION OF DELAWARE PATENT OFFICE OF OFFENBAOH-ON-THE-MAIN, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, ING., OF NEW YORK, N. Y., A CORPORA- MANUFACTUBE OF NEW AZODYESTUFFS No Drawing. Application filed August 27, 1928, Serial No. 302,439, and in Germany September 5, 1927.

= We have found that new and valuable azodyestuffs are obtained by combining any diazo-, tetrazoor diazoazocompound containing no free sulfonic nor carboxylic acid groups with bis- (2hydroxy-3-naphthoyl) arylene-lA-diamines containing one substituent each in ortho position to the aminogroups and corresponding probably to the general formula wherein X and Y, being equal or different, mean substituents of the group comprising alkyl, alkoxy and halogen.

The new dyestuifs of the probable general formula wherein X and Y have the aforesaid signification and Z means the residue of any diazo, 1etrazo-, or diazoazo-compound of the benzene-, naphthalene or anthraquinone series containing no free sulfonic nor carboxylic acid groups, are when dry reddish to blackish powders, soluble in concentrated sulfuric acid with a bluish-red to bluish-green color. hen mixed with the usual substrata they yield valuable color lakes. When produced on the vegetable fiber by the ice-color method,

substituted li-aryldiamines, for instance by heating these components with a dehydrating agent in a suitable organic diluent as indicated in U. S. Patent 1,101,111.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade'degrees, but it is understood, that our invention is not limited to the particular products or reacting conditions 'mentioned therein.

Example 1 A diazosolution.preparedin the usual manner from 16.2 parts of 2.5-dichloraniline, is combined with a solution in a dilute caustic soda solution of 27 parts of bis- (2-hydroXy-3-naphthoyl) I 2.5-diamino-4chloro-1-anisole, containing turkey red oil and a sufficient amount of sodium acetate for neutralizing the excess of the mineral acid. Theseparated dyestuif corresponding probably to the formula Q no 01 on /OOH; o o-NH-Q-NH-o o I v d is filtered off and well washed. It represents when dry a dark powder and dissolves in concentrated sulfuric acid with a wine-red tint. It may be advantageously used in form of a paste and yields, when mixed with a substratum in the usual manner, a brown lake of a very good fastness to light.

In order to produce a dyestufi of this kind on the fiber one may proceed as fellows:

Example 2 Well boiled and dried cotton yarn is impregnated in a solution, containing 5 grs. of his (2-hydroXy-3-naphthoyl) 2.5 diamino- 4-chloro-l-toluene, 10 cc. of a caustic soda solution of 34 B. and 8 cc. of Turkey red OCH;

oil per liter, well wrung out and developed with a diazosolution containing 3.2 grs. of 4-chloro-2-amino-l-anisole per liter and being neutralized with sodium acetate. Then it is rinsed, soaped and dried.

In this manner a red, claret-like dyeing of a good fastness to light and to kier-boiling is obtained.

The dyestufi thus produced on the fiber corresponds probably to the formula OCH3 o OH om o O-NH-QNH- o o Example 3 Ewample 4 Cotton yarn previously well treated is padded in the usual manner with a solution containing 5 grs. of bis- (2-hydroXy-3-naphthoyl)-2.5-diamino-4-chloro-1-anisole, 10 cc. of caustic soda solution of 34 B. and 8 cc. of Turkey red oil per liter, and developed with a diazo solution containing 8.4 grs. of 5-nitro-i2-amino-1-anisole per liter.

In this manner a dark garnet dyeing of a good fastness to light is obtained. The dyestuff thus produced on the fiber corresponds probably to the formula OCH; HO- 0 onwGnn-o o- In the same way our process is carried out when starting from other 2-hydroXy-3-naphthoic acid arylamides of the constitution described herein and from other diaZ0-, tetrazoor diazoazo-compounds.

The new dyestuffs may also be prepared by the printing process according to one of the usual methods.

OCH;

The following table shows the vention shades of to our in- Diazocompound from- Combined with Shade m-chloroaniline bis- (2-hydroxy-3-naph- Claret.

thoyl)-2.5-diamino1.4- xylole. 2.5-dichloroanillne .do Red-brown. 4-chloro-2-toluidine. Claret. 4-nitro-2-toluidine. Red-brown. 5-n1tro-2toluid1ne. Garnet. 4-nitro-2-anisidine Y e l 1 o w is h claret. 5-nitro-2-anisidine Garnet. 4-chloro-2-anisidine. Claret. o-aminoazotoluene Dark bluish- 4 garnet. 2.5-dich1oroan1hne b1s-(2-hydroxy-3'-naph- Y all 0 w i s h thoyl) -2.5-diar nino-hybrown. droquinoned1rnethy1- ether. 3.5-dichlor n do Brown. 4-nitro-3-chloroaniline- -do Dark-brown. m-xylidine bis-(2-hydroxy-3-naph- Full red.

thoyl)-2.5-d lamino-1.4- dichlorobenzene. ZH-Chlornanilme rin Yelllowish-Scaret. 2.5-dichloroaniline Yellowish-red. 4-chloro-2-toluidined, 5-chloro2-to1uidine Full red 4-chloro-2-anisidin Claret 5-nitro-2-toluidine 3njtro-4-toluidine 4-chloro-2-nitroanil fi-nitro-iranisidine o-aminoazotoluene. a-arninoanthraquinone rn-chloroaniline 5-ehloro-2-toluidine 4-nitro-2-t0luidine a-aminoanthraqurnone. m-xylidine 4-chloro-2-toluidine 4-chloro-2-nitroaniline 4-chloro-2-anisidine 3-nitro-4-toluidine 5-nitro-2-toluid1ne o-aminoazotoluene m-xylidine 5-nitro-2-anisidine.

3-nitro-4-toluidine Dianisidine (1 mol.)

o-phenetole-azo-a-naphthylamine. rn-xylidine rn-chloroaniline 2. 5-dichloroaniline 4-ch1oro-2-toluidine 5-chloro-2-toluidine. 4-chloro-2nitroaniline 4-nitro-2-toluidine 5nitro-2-toluidine 3-nitro-4-toluidine.

bis- (2-l1ydroxy-3 naphthoyl) 2. 5 diarnlno 4 methoxy-toluene.

bis (2-hydroxy 3 naphthoyl) 2.5 diainino 4 chlorotolnene.

5-nitro-2-anisidine o-anunoazotoluene a-aminoanthraquinone Yellowisliclaret. W1ne-red.. Brownish-red.

Garnet.

Dark-violet. Full red. Brown-red.

Yellowish-scar- Brownish-red.

Claret.

Brownish-rcd.

R e d d i s h brown.

Full claret.

Garnet-brown.

Dark reddishbrown.

Dark browngarnet.

Garnet.

Dark brown. Dark brown. Garnet. Bluish-red. Dark-violet. Dark claret. Dark brown. Browngarnet. Garnet-brown. R e d d i s h brown.

Dark brownish garnet.

Dark garnet.

(' A i t e r c o p pered) dark navy-blue.

violet- Dark-red.

Brown-red.

Brownish-red. Full red.

I Claret-red. Dark claret.

Brownish-red.

Brown-claret. Claret. Garnet.

Dark bluish garnet. Yellowish-clar- We wish it to be understood that the term manufacturing in the following claims diazoazo-compounds.

We claim: 1. As new products azo dyfestufi'scorresponding probably to the general formula wherein Xas well as Y means alkyl, alkoxy or halogen and Z means the residue of anydiazo-compound, of the benzene, napthalene or anthraquinone series containing no .free sulfonic nor carboxylic acid group, which '1 products are when dryreddish to blackish ipoWders, solublein concentrated sulfonic acid with a bluish-red to bluish-green color,

being suitable for the production of valuable color lakes and yielding, when produced on the vegetable fiber, dark red to black dyeings and printings of a remarkable fastness to light. 2. Textile materials claimed in. claim 1.

3. As new products azodyestufis corresponding probably to the general formula dyed with the dyestuli's wherein Z means the residue of any diazocompound of the benzene, napthalene or anthraquinone series containing no free sulfonic nor carboxylic acid groups, which products are when dry reddish to blackish powders, suitable for the production of valuable color lakes and yielding, when produced on the vegetable fiber red to brown dyeings and printings of a remarkable fastness to light.

4. Textile materials dyed with the dyestuffs claimed in claim 3,

5. As new products, azo-dyestufi's corresponding probably to the general formula wherein X X and X mean hydrogen atoms of which one or two may be replaced by halogen, a nitro-,1nethylor alkoxy-group, Which products are when dry reddish to blackish powders, suitable for the production of Valuable color lakes and yielding, when produced on the vegetable fiber, red to brown dyeings and printings of a remarkable fastness to light.

6. Textile materials dyed with the dyestuffs claimed in claim 5.

7. As new products, azo-dyestufi's corresponding probably to the general formula wherein X means CH or OCH or hydro gen, X hydrogen or chlorine or CH one X hydrogen and the other N0 but at least two of the four Xs being hydrogen, which products are when dry reddish to blackish powders, suitable for the production of valuable color lakes and yielding, when produced on the Vegetable fiber, red to brown dyeings and printings of a remarkable fastness to light.

8. Textile materials dyed with the dyestuffs claimed in claim 7.

In testimony whereof, we alfix our sign-atures.

LEOPOLD LASKA. ARTHUR ZITSCHER. 

